LONG-TERM TRANSFORMATION AND REDISTRIBUTION OF

POTENTIALLY TOXIC HEAVY METALS IN ARID-ZONE SOILS:

II. INCUBATION AT THE FIELD CAPACITY MOISTURE CONTENT
FENG XIANG HAN and AMOS BANIN
Department of Soil and Water Sciences, The Faculty of Agricultural, Food and Environmental
Sciences, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 76100, Israel
( author for correspondence, e-mail: banin@agri.huji.ac.il)

(Received 19 June 1997; accepted 10 September 1998)

Abstract. Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils
incubated in the field capacity moisture regime for one year, were studied. The heavy metals were
fractionated into six empirically defined fractions using a selective sequential dissolution (SSD)
protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil
component targeted for dissolution during the specific SSD step, but it is not assumed that they
are mineralogically and chemically totally specific. The transformations of the metals in the two
soils incubated at the field capacity regime were compared with those at the moisture saturation
regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the
exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb,
Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred
during the fractionation and within one hour after addition. This was followed by a second stage,
involving long-term transformation processes of all metals: added Cd was transferred from the EXC
into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was
transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were
transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO
fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime,
Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent
the same transformation pathways during the slow long-term process, with slightly different rates,
in both water regimes. At low levels of addition, the incubated soils moved over one year towards a
distribution similar to that of the native soil. At higher levels, the soils still remained removed from
the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.
Keywords: arid-zone soils, field capacity, fractionation, heavy metals, kinetics, redistribution, transformation

1. Introduction
Heavy metals added to soils by various processes, pose environmental risks of
contamination of soil and groundwater and introduction into the food-chain. The
increased use of reclaimed sewage water for irrigation, the disposal of waste-water
sludge and of municipal and industrial refuse, and increased atmospheric fallout
result in magnified loads of heavy metals onto soils. In the soil, metals tend to partition among the solid and solution phases, with high preference to the solid-phase.
Water, Air, and Soil Pollution 114: 221250, 1999.
1999 Kluwer Academic Publishers. Printed in the Netherlands.

222

F. X. HAN AND A. BANIN

Furthermore, metals partition among the solid phase components, including the
exchangeable complex (EXC), carbonate (CARB), oxides (easily reducible oxidesERO, e.g., Mn oxides, and reducible oxides-RO, e.g., Fe oxides), organic matter
(OM) and residual (RES) component. Metal partition in the solid phase of soils is
customarily measured by sequential selective dissolution (SSD) procedures. These
procedures entail a sequence of chemical extraction steps, designed to selectively
dissolve or extract a single solid-phase component (Tessier et al., 1979; Sposito
et al., 1983; Emmerich et al., 1982; Beckett, 1989; McGrath and Cegarra, 1992;
Han and Banin, 1995). The released elements are then referred to as bound to
the targeted component. The selective extraction procedure at each step has some
problems in selectivity, specificity of its regents and extraction. Thus, the name
customarily used for each fraction is meant only for identification purposes and
it is not intended to fully define it mineralogically and chemically. Still, the SSD
procedure supplies more valuable information on the forms, availability, mobility
and transformations of heavy metals in the solid-phase components of soils and
sediments, than any single extraction protocol. In the present series we employ
an optimized SSD procedure to follow elemental transformations in soils amended
with metals and incubated under controlled moisture regimes for prolonged periods
of time. Following metal addition in a labile chemical form, a long-term process
of redistribution is set in the soil, driven by the tendency of the system to return to
chemical equilibrium, but limited by the kinetics of the involved reactions.
On the basis of the findings in Part I of this series (Han and Banin, 1997),
we have suggested that long-term transformation of added heavy metals in watersaturated soils was the result of two opposite processes: The mobilization of the
native metals due to mild chemical reduction after saturation of the soil on one
hand, and the immobilization of the added heavy metals due to their transfer from
the more labile fractions into the stable fractions on the other hand. Much attention
was given to the study of heavy metal transformation in water-saturated soils, and
it was found that due to lowered redox potential in the soil, reduction of Fe and
Mn from their oxides takes place causing heavy metals redistribution among the
solid-phase components (Silviera and Sommers, 1977; Schwab and Lindsay, 1983;
Mandal and Mandal, 1986; Hazra et al., 1987; Banin et al., 1990; Patrick and Jugsujinda, 1992; Han and Banin, 1996; 1997). Smaller effort was devoted to the study
of processes in unsaturated soils under controlled conditions. Silviera and Sommers
(1977) reported that the transformations of Cu, Zn and Cd (i.e., increase of DTPAextractable forms with time), and Pb (i.e., constant DTPA-extractable Pb with
time) were similar in water-saturated and unsaturated (at 1/3 bar water tension)
soil-sludge systems. Mann and Ritchie (1994) studied the transformation of added
soluble Cd in western Australian soils incubated at the field capacity regime under
controlled conditions, and reported that added Cd was transformed from soluble to
less soluble fractions with time, depending upon the type of soil, soil pH and rate of
application: in a sandy soil, Cd was transformed from the soluble to exchangeable;
in lateritic podzolic soils, from the exchangeable to organic matter fraction, es-

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

223

pecially at higher pH; in soils dominated by goethite from the exchangeable to the
oxide and residual fractions. Observations under field conditions showed that heavy
metals added to soils were transferred with time from the more labile fractions
into the less labile fractions. Sposito et al. (1983) reported that heavy metals in
the EDTA-extractable fraction (possibly carbonates) and/or the HNO3 -extractable
fraction (associated with resistant secondary minerals) in sludge-amended soils in
California tended to increase with time. McGrath and Cegarra (1992) found that Ni
and Zn in the exchangeable and NaOH-extractable fraction (primarily organically
bound) and Cd in the exchangeable fraction decreased, and metals in the residual
fraction increased, while Cr fractionation changed only slightly during the 20 yr
after cessation of sludge application to field plots in England. Copper applied as
copper sulfate in lateritic sandy soils was initially bound to the organic fraction
and was transferred slowly to the residual fraction over the study period of 20
yr (Mclaren and Ritchie, 1993). Payne et al. (1988) found that following eight
annual applications of Cu-sulfate and Cu-enriched manure to field-soils, copper
was mainly bound to the organic and oxide associated fractions. Mullins et al.
(1982) reported that 3 yr of continued application of Cu-enriched manure increased
the organically bound, followed by oxides bound fractions. Soon (1994) reported
that agricultural crop production for 23 yr resulted in the transformation of Zn
from the exchangeable organically-bound fractions to the hydrous oxide-associated
fractions. Han et al. (1995) found that added Zn in calcareous soils was transformed
from the amorphous Fe oxide fraction into the crystalline Fe oxide fraction.
The present study investigated the pathways and kinetics of transformations of
native and added Cd, Cr, Cu, Ni, Pb and Zn in two arid-zone soils during a period
of one year of controlled incubation at the field capacity water regime. This report
compares the transformation of heavy metals in arid-zone soils incubated under
controlled conditions in the field capacity regime with those in the saturated-paste
water regime reported earlier (Han and Banin, 1997).

2. Materials and Methods

2.1. S OILS
Bulk samples of topsoils (020 cm) were collected from two cultivated areas in
Israel: A sandy soil from a site in the coastal plain (Beit-Yizhak, near Netanya),
and a loessial soil from a site in the south (Chavat Ram, near Beersheva). Soil
samples were air-dried, ground and screened through a 2 mm sieve. Selected proporties of the soils were reported by Han and Banin (1996; 1997). The sandy soil
contained low carbonate (0.5%) and had low cation exchange capacity (CEC) and
spefic surface area (SSA) due to its sandy texture. The loessial soil had a loamy
texture, intermediate carbonate content (23.2%) and intermediate CEC and SSA.
Both soils had low organic matter content (1.031.42%). The pH of the saturated

224

F. X. HAN AND A. BANIN

paste of the soils was 7.15 and 8.03 for the sandy and loessial soils, respectively.
The total native contents of heavy metals in the soils are given in Table I.
2.2. I NCUBATION

EXPERIMENT

The experiment was designed to study the transformation and repartition of six
metals (Cd, Cu, Cr, Ni, Pb and Zn) added together at different loading levels, to
two soils (Table I). The changes in native metal partitioning in control samples
were measured as well.
Metals were added at levels related to their total native contents (T) in the
soil (Table I). In the sandy soil, Cd, Cr, Cu, Ni, Pb and Zn were each added at
rates designated as Ck(0T), 0.5T, 2T, 3T, and 5T. In the loessial soil, metals were
added at the rates of Ck(0T), 0.5T, 3T. and 5T. Soil aliquots (one kg d.w.), were
thoroughly mixed in plastic pots with the designated mixture of dry metal-nitrate
salts and then sprayed with deionized water to bring their moisture content to the
field capacity level (0.12 and 0.14 kg water kg1 soil for the sandy and the loessial
soils, respectively). Each treatment was replicated in two pots.
The soils were incubated in a controlled-temperature room at 251 C. Subsamples were taken from each pot for selective sequential dissolution fractionation
analyses (SSD) prior to wetting (time zero), and after 1 hour, 1 day, and 1, 3, 6, 12,
24, and 48 weeks.
During incubation, pots were loosely sealed with a cap to diminish evaporation.
However, slow gas exchange with the atmosphere was permitted. Before samples
were taken for fractionation analysis, the soil was thoroughly mixed to ensure
homogeneity of the soil. At the same time, a subsample was taken to determine
the soil moisture content. Deionized water was added to the remaining soil in the
pots, to maintain the moisture level at the field capacity. Analysis showed that the
moisture content of both soils remained fairly constant throughout the experiment:
the average was 0.105 0.008 kg kg1 for the sandy soil, and 0.151 0.009 kg
kg1 for the loessial soil during the 48 weeks of incubation.
2.3. C HEMICAL

ANALYSES

The procedures of sequential selective dissolution (SSD), total metal content by

HNO3 digestion (TOT-HNO3) and by HF digestion (TOT-HF) were described in
detail in Banin et al. (1990) and Han and Banin (1995, 1996, 1997). A summary
of the SSD protocol is given in Table II. Multi-elemental analyses in soil extracts
were conducted by ICP-AES (Han and Banin, 1997).
2.4. DATA A NALYSES
The following parameters were used to describe the transformation kinetics of
metals in soil (Banin et al., 1990; Han and Banin, 1997):

Treatment
designation

Cda

Cr

0.050.00
0.180.028

14.750.14
29.770.76

Soil

Treatment
Class

Sandy
Loessial

Native
Native

Sandy

Control
Low
Intermediate
High

CK
0.5T
2T
3T
5T

0.00
0.05
0.17
0.31
0.52

Loessial

Control
Low
High

CK
0.5T
3T
5T

0.00
0.09
0.54
0.90

Cu
Ni
Pb
1
Metal contents in native soils (mg kg ) (n=4)

Zn

10.20.10
6.90.05
13.90.13 17.90.13
Metal added (mg kg1 )

14.420.44
14.570.33

31.00.58
39.70.16

0.00
7.38
23.79
44.25
73.75

0.00
5.10
16.45
30.60
51.00

0.00
3.43
11.06
20.58
34.30

0.00
6.21
20.03
37.26
62.10

0.00
15.51
50.02
93.03
155.05

0.00
14.89
89.31
148.85

0.00
7.50
45.00
75.00

0.00
10.76
64.56
107.60

0.00
8.44
50.61
84.44

0.00
20.92
125.49
209.20

a Analytical problems related to the very low native concentration of Cd in the sandy soil, lead to the fact that additions of Cd are

not at the exact proportionality to the total content in the native soil (T), as are the other metals in the same treatment class.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

TABLE I
Natural concentration (HNO3 -extractable) in native soils (average and standard deviation) and levels of addition of metals to the
two soils

225

226

TABLE II
Protocol for selective sequential dissolution (SSD) procedurea
Fraction

Targeted
component

Reagents

pH

Ratio of
solution/soil

Temperature
( C)

Time

1
2
3

EXC
CARB
ERO

25:1
25:1
25:1

25
25
25

30 min
6 hr
30 min

OM

25:1

80

3 hr

Water bath

RO

Reducible oxides

25:1

90

3 hr

Water bath

RES

Residual

1 M HN4 NO3
1 M NaOAc-HOAc
0.04 M NH2 OH. HCl
+ 25% HOAc
30% H2 O2
+ 0.01M HNO3
0.04 M NH2 OH. HCl
+ 25% HOAc
4 M HNO3

7
5
2

Exchangeable
Carbonate
Easily reducible
oxides
Organic matter

25:1

180

30 min

Microwave

a Following: Banin et al. (1990); Han and Banin (1997).

Note
F. X. HAN AND A. BANIN

Step
No.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

227

Partition Index of element, I, and the reduced Partition Index, IR ,

I=

k
X

(Fi (i)n )

(1)

i=1

IR = I /(k n )

(2)

where i is the extraction step number (1: least aggressive, k: most aggressive) with
the following values assigned to i in Equation (1) to represent the various steps and
components: EXC = 1; CARB = 2; ERO = 3; OM = 4; RO = 5; and RES = 6. Fi is
the fractional content of the element in component i out of its total extracted, and
n is an integer (usually 1 or 2). In our case, k equals 6 and n equals 2; thus minimal
IR = 0.03 and maximal IR = 1. This parameter was introduced to quantitatively
describe the relative binding intensity of metals in soils and enable the comparison
of the binding intensity of a given metal among soils, and of different metals in the
same soil. The value of i in Equation (1) increases in accordance with the gradual
increase in the aggressiveness of extractants used in the sequential steps of the SSD
procedure. Thus, a low value of IR (close to the minimum), represents a distribution
pattern where much of the metal resides in the EXC fraction, whereas a high value
(close to 1) results from a situation where a high proportion of the metal is bound
in the RES fraction. Intermediate values represent various patterns involving metal
partitioning among all the solid-phase components.
Utf , the fractional attainment of soil equilibrium was defined as (Banin et al.,
1990):
Utf = Fa /Fc

(3)

where Fa is the fraction of the metal bound to a given component in a metalamended soil after incubation for a given time, and Fc is the fraction of the metal
bound to the same component in the native (control) soil, at incubation for the same
time. Utf is used to describe the approach of the fractional content of the metal in
the amended soil to the quasi-equilibrium state found in the non-amended soil.
Ut s , the whole-soil attainment of equilibrium for a given metal, was defined as
the sum, for i = 1 to k, of the products of the fraction of a metal bound to a given
component by its Utf :
Ut s =

k
X
(Fi Utf i )

(4)

i=1

where Utf i is the Utf function value of a given solid-phase component. Ut s (Utsoil)
was designed to describe by a single parameter the removal from, or attainment of,
equilibrium of the incubated metal-amended soil in comparison to the incubated
non-amended control soil. By definition, Ut s of each metal in the non-amended

228

F. X. HAN AND A. BANIN

TABLE III
Estimated recovery (%) (average and standard deviation, 2 replicates) of added metals in two-arid-zone
soils
Soil

Treatment

Cd

Cr

Cu

Ni

Pb

Zn

Sandy

0.5T
2T
3Tb
5T

12038a
80.87.4
73.3
86.06.6

90.54.4
94.61.1
97.0
92.64.5

11118
1033.0
102
1015.0

1123.4
1040.6
103
10310.0

99.812.0
12713.4
92.3
88.79.9

97.01.7
1001.8
100
99.86.7

Loessial

0.5T
3Tb
5T

NAc
87.5
80.00.6

88.61.0
80.0
78.54.3

96.00.6
102.6
98.34.5

1062.7
102.1
1014.5

91.411.0
74.0
83.44.1

98.27.7
103
96.44.7

a Recovery (%) = [Measured total concentration (TOT-HNO )] 100/[calculated native + added con3

centration]. The total metal contents in the soils were measured after 12 weeks of incubation.
b Only one measurement was made in this treatment.
c Data not available.

soil equals one, while in the metal-amended soils it is initially larger than one, and
slowly tends to decrease with time and converge towards one.

3. Results and Discussion

3.1. M ETAL

RECOVERIES BY THE

SSD

ANALYSES

As a basis for the discussion of the slow transformations of the metals in the
amended soils, it is necessary to assess (a) the recovery of added metals by the
total analysis (TOT) and by the SSD procedure (SSD-Sum), and (b) the variability
of extracted metals from each fraction with time, as compared to the variability of
their Sum with time.
The estimated total recoveries of added Cu, Ni and Zn in both soils, and Cr and
Pb in the sandy soil ranged from 90 to 110% (Table III). Slightly low recoveries
(8090% of added) were observed for Cd in both soils and for Cr and Pb in the
loessial soil.
In general, the analyses by the sequential selective dissolution procedure gave a
reasonable degree of analytical reproducibility and metal recovery (Sum). To assess
reproducibility, we employ the coefficients of variation (CV(%) = std deviation
100/average) for the whole experimental period instead of the traditional variance
between replicates. The variability of the sum of most of the metals (Cr, Cu, Zn
and Ni) was relatively small and the yearly coefficient of variation values were
mostly smaller than 5% (Figures 1 and 2). The sum of extracted Pb and Cd had
higher CV(%) values of 520% and 2040%, respectively. This variability, mostly

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

229

Figure 1. The coefficient of variation (CV% = standard deviation 100/average) of six metals in the
fractions and the Sum of metal extracted by repeated SSD procedures over one year from the sandy
soil (Ck, 0.5T, etc., are treatments, T: the total content of native metal in soil).

encountered in the untreated soils and those receiving low loads of Pb and Cd, is
attributed to analytical problems at low metal concentrations. On the other hand,
the changes of metal concentrations in the individual fractions in the two soils
during the period of one year, were large and their coefficients of variation were
much larger than those of their sum (Tables IV and V; Figures 1 and 2). If the
CV(%) of metal content in individual fractions are large and those of their sum
are small, the SSD analyses are satisfactory, and the results show that the metal
concentrations in the individual fractions changed significantly while the sum of

230

F. X. HAN AND A. BANIN

Figure 2. The coefficient of variation (CV%) of six metals in the fractions and the Sum of metal extracted by repeated SSD procedures over one year from the loessial soil (Ck, 0.5T, etc., are treatments,
T: the total content of native metal in soil).

the metal extracted by the SSD procedure remained relatively constant over the
whole year of incubation. Thus, the larger CV(%) of metal concentration in each
fraction, and the relatively small CV(%) of their sum, indicate significant metal
redistribution over the period of one year of incubation.
The relative errors (RE(%)) between the sum of Cu, Cr, Ni and Zn extracted by
the SSD procedure, and their total content (TOT), were mostly smaller than 10
15% (Tables IV and V). Re(%) values for Cd and Pb were higher, mainly due to
limit-of-detection and analytical problems in the ICP-AES analyses.

TABLE IV

Metal

Treatment

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

Total

RE(%)b

Cda

0.5 T

average
stdev
average
stdev
average
stdev
average
stdev

0.067
0.037
0.032
0.032
0.053
0.039
0.061
0.050

0.069
0.030
0.149
0.051
0.228
0.057
0.349
0.053

0.048
0.053
0.032
0.031
0.018
0.026
0.031
0.051

0.031
0.035
0.034
0.034
0.067
0.066
0.069
0.064

0.019
0.029
0.015
0.022
0.013
0.023
0.050
0.064

0.019
0.024
0.022
0.027
0.007
0.012
0.022
0.028

0.252
0.106
0.284
0.116
0.386
0.122
0.582
0.114

0.12

114.91

0.18

55.92

0.30

28.17

0.49

19.55

average
stdev
average
stdev
average
stdev
average
stdev
average
stdev

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.01
0.03
0.70
0.30
2.11
0.72
4.24
1.30
6.85
1.56

0.02
0.02
0.39
0.25
1.49
0.63
2.88
1.15
4.20
1.50

3.04
0.24
8.56
0.49
22.09
0.63
39.02
1.99
57.73
3.26

1.62
0.28
2.31
0.34
3.73
0.55
5.45
0.26
6.80
0.63

9.24
0.47
9.00
0.38
9.11
0.58
9.74
0.66
10.15
0.55

13.94
0.70
20.95
0.82
38.53
1.54
61.31
1.59
85.73
2.05

14.62

4.66

20.02

4.65

36.47

5.65

57.16

7.26

81.99

4.56

2T
3T
5T

Cr

Ck
0.5T
2T
3T
5T

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

The average and standard deviation of metal content (mg kg1 ) in each fraction and their sum as extracted by the SSD
procedure from the sandy soil during one year of incubation, and its comparison with the total content of metal in the
soil. [n (number of observations) = 8]

231

232

TABLE IV
Continued.
Treatment

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

Total

RE(%)b

Cu

Ck

average
srdev
average
srdev
average
stdev
average
stdev
average
stdev

0.04
0.04
0.12
0.06
0.27
0.17
0.57
0.43
1.08
0.62

0.33
0.15
1.08
0.18
3.67
0.56
8.53
0.97
14.85
1.64

0.14
0.09
0.43
0.18
1.49
0.57
3.15
1.06
5.02
1.58

1.26
0.11
2.60
0.24
6.12
0.43
10.98
0.39
17.18
1.06

4.49
0.38
6.72
0.53
9.82
0.68
13.26
1.32
15.50
1.15

3.07
0.33
3.34
0.27
3.95
0.78
4.70
0.72
4.94
0.64

9.34
0.32
14.29
0.63
25.32
1.44
41.19
1.85
58.57
2.65

9.92

5.86

16.96

15.71

27.37

7.48

41.81

1.47

61.70

5.08

average
stdev
average
stdev
average
stdev
average
stdev
average
stdev

0.07
0.09
0.13
0.11
0.62
0.37
1.77
1.06
3.68
1.72

0.43
0.14
1.44
0.47
4.69
0.91
9.63
1.24
14.52
1.05

0.20
0.32
0.95
0.42
2.90
0.94
4.92
1.38
6.53
1.65

1.47
0.29
2.68
0.36
4.58
0.48
6.20
0.59
9.04
0.76

0.71
0.18
0.81
0.24
0.98
0.25
1.25
0.18
1.48
0.33

4.07
0.23
4.00
0.31
3.97
0.33
4.01
0.27
4.07
0.25

6.95
0.65
10.02
0.88
17.74
1.01
27.77
0.87
39.32
1.64

7.96

12.63

11.53

13.12

18.72

5.23

28.29

1.85

42.24

6.90

0.5T
2T
3T
5T

Ni

Ck
0.5T
2T
3T
5T

F. X. HAN AND A. BANIN

Metal

TABLE IV
Continued.
Treatment

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

Total

RE(%)b

Pb

Ck

average
stdev
average
stdev
average
stdev
average
stdev
average
stdev

0.13
0.24
0.03
0.08
0.12
0.34
0.05
0.10
0.17
0.44

0.79
0.50
3.34
1.73
11.42
1.30
21.83
1.00
34.67
1.82

1.27
0.63
1.98
0.52
4.54
1.96
7.20
2.52
8.74
3.48

2.08
0.27
3.25
0.46
5.36
0.56
8.23
0.92
10.26
1.07

3.44
0.90
4.74
0.73
6.18
1.19
7.68
1.24
9.76
0.57

3.89
2.12
4.44
2.13
4.98
2.50
5.41
2.24
6.99
2.55

11.60
1.93
17.77
2.41
32.60
1.90
50.41
2.58
70.58
5.00

12.93

10.26

18.59

4.41

41.26

21.00

45.87

9.89

66.10

6.78

average
stdev
average
stdev
average
stdev
average
stdev
average
stdev

0.00
0.01
0.04
0.08
1.96
1.36
6.21
3.29
13.81
5.56

6.67
0.63
17.01
1.55
40.97
3.86
69.87
5.22
101.90
8.25

3.57
0.53
6.12
0.89
11.04
1.96
16.12
2.62
20.92
3.97

1.96
0.55
3.73
0.73
7.54
1.14
11.78
2.78
16.91
4.27

6.47
0.62
7.45
0.67
7.92
0.95
8.91
1.09
9.43
1.62

9.62
1.48
8.95
0.79
8.88
0.79
10.00
1.91
9.70
0.62

28.30
1.93
43.29
1.54
78.30
3.00
122.90
2.07
172.67
6.97

28.56

0.91

45.13

4.07

81.53

3.97

124.14

1.00

185.72

7.03

0.5T
2T
3T
5T

Zn

Ck
0.5T
2T
3T
5T

233

a Data on Cd in the native soil are not presented here due to analytical problems related to the very low concentrations.
b RE (%): (Sum-Total) 100/Total.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

Metal

234

TABLE V
The average and standard deviation of metal content (mg kg1 ) in each fraction and their sum as extracted by the SSD
procedure from the loessial soil during one year of incubation, and its comparison with the total content of metal in the soil.
[n (number of observations) = 8]
Metal

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

0.5T

average
stdev
average
stdev
average
stdev

0.041
0.026
0.060
0.039
0.082
0.044

0.130
0.061
0.628
0.169
0.977
0.294

0.037
0.063
0.060
0.069
0.061
0.084

0.023
0.028
0.032
0.019
0.046
0.035

0.037
0.065
0.015
0.023
0.041
0.044

0.067
0.089
0.078
0.098
0.046
0.059

0.335
0.165
0.873
0.315
1.254
0.437

average
stdev
average
stdev
average
stdev
average
stdev

0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01

0.65
0.19
2.73
0.42
14.10
3.93
21.97
5.47

0.14
0.09
1.56
0.32
9.14
1.28
15.34
2.71

1.77
0.28
8.72
0.97
43.32
4.89
67.73
6.47

2.06
0.33
3.34
0.40
11.98
2.01
18.72
2.88

27.37
1.47
28.15
1.47
32.93
1.20
38.03
2.32

31.99
1.29
44.50
1.47
111.48
3.94
161.80
3.99

3T
5T

Cr

Ck
0.5T
3T
5T

Total

RE(%)b

0.63

38.54

0.95

31.84

29.17

9.66

39.55

12.51

98.28

13.43

140.15

15.45

F. X. HAN AND A. BANIN

Treatment

Metal

Treatment

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

Total

RE(%)b

Cu

Ck

average
stdev
average
stdev
average
stdev
average
stdev

0.03
0.03
0.35
0.20
4.32
1.62
10.43
5.71

4.52
0.65
6.80
0.31
23.01
2.23
36.86
1.986

0.25
0.08
1.36
0.30
7.84
1.97
12.84
3.30

0.13
0.07
0.45
0.10
1.85
0.52
3.13
0.70

2.68
0.33
5.02
0.54
12.96
1.16
16.35
1.89

7.91
0.46
9.79
0.65
12.96
0.98
15.25
1.32

15.52
0.59
23.77
0.64
62.94
1.66
94.86
2.06

13.37

16.10

20.49

16.01

60.39

4.23

87.35

8.59

average
stdev
average
stdev
average
stdev
average
stdev

0.02
0.04
0.49
0.26
4.14
3.07
7.93
6.78

5.06
0.75
10.24
0.99
34.63
4.18
53.57
8.39

1.16
0.37
3.94
0.84
13.36
3.00
21.55
5.56

1.24
0.22
2.69
0.61
9.17
2.62
13.96
4.30

4.10
0.60
5.15
0.64
9.62
1.56
12.39
2.79

14.09
1.06
14.90
0.98
16.70
1.73
19.13
1.45

25.68
1.34
37.41
1.55
87.61
2.73
128.54
4.25

22.34

14.95

30.47

22.77

84.21

4.04

126.98

1.23

0.5T
3T
5T

Ni

Ck
0.5T
3T
5T

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

TABLE V
Continued.

235

236

TABLE V
Continued.
Treatment

Parameter

EXC

CARB

ERO

OM

RO

RES

Sum

Total

RE(%)b

Pb

Ck

average
stdev
average
stdev
average
stdev
average
stdev

0.03
0.08
0.11
0.21
0.07
0.11
0.02
0.06

9.94
2.81
13.74
1.73
40.14
7.00
59.93
3.24

0.09
0.18
1.44
0.48
7.33
1.58
11.30
2.78

0.04
0.10
0.05
0.10
0.43
0.36
0.45
0.26

1.09
0.63
2.88
0.73
8.76
1.87
11.37
1.83

6.97
2.97
9.20
0.83
12.30
2.73
16.89
1.50

18.17
3.77
27.42
2.63
69.03
7.63
99.96
5.43

19.45

6.61

21.03

30.38

48.24

43.10

82.52

21.13

average
stdev
average
stdev
average
stdev
average
stdev

0.00
0.01
0.00
0.00
1.28
1.23
3.40
2.88

9.41
3.74
16.02
3.15
67.52
7.19
113.59
13.12

0.61
0.29
6.84
1.17
35.44
4.70
54.17
8.23

0.04
0.08
0.25
0.46
3.15
1.24
5.35
1.72

5.23
0.69
10.22
1.36
24.14
4.13
30.40
5.10

27.95
2.17
30.56
1.33
37.02
3.58
43.59
3.10

43.26
5.53
63.89
5.27
168.55
7.03
250.49
7.65

43.64

0.88

59.55

7.29

169.50

0.56

240.06

4.35

0.5T
3T
3

5T

Zn

Ck
0.5T
3T
5T

a Data on Cd in the native soil are not presented here due to analytical problems related to the very low concentrations.
b RE(%): (Sum-Total) 100/Total.

F. X. HAN AND A. BANIN

Metal

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

3.2. D ETAILED

237

ANALYSIS OF SINGLE METAL BEHAVIOR DURING INCUBATION

Since the sums of metal fractions extracted by the SSD analyses conducted over
the experimental period were fairly constant, it is more convenient to use fractional
distribution patterns to study the redistribution of metals with time after amendment. From now on, we will use the percentages of metals in fractions, instead
of their absolute concentrations, to follow the redistribution trends observed in
the incubated soils (Figures 38). In addition, the IR (Equation (2); Figure 9) and
Ut s (Equation (4), Figure 10) parameters will be used to describe and analyze the
redistribution processes.

3.2.1. Cadmium
Native and added Cd was mainly bound to the CARB fraction (Figure 3), and this
metal had the lowest IR among the six metals (Figure 9). During incubation at
the field capacity regime, added Cd was transferred from the EXC fraction into the
CARB fraction. This process is the same as that of Cd in soils incubated at moisture
saturation (Han and Banin, 1997). It appears that the water regime did not change
the direction and pathways of transformation of Cd in these soils. Cadmium rapidly
redistributed in the amended soils even at higher levels of addition and acquired a
typical distribution dominated by its presence in the CARB fraction. This indicates
that the added Cd remains relatively labile. Similar behavior was observed earlier
in arid-zone soils amended with soluble salts in the saturated regime (Banin et al.,
1990; Han and Banin, 1997) and in sludge-amended soils in the field (Emmerich
et al., 1982; McGrath and Cegarra, 1992).

3.2.2. Chromium
In the untreated soils Cr was mostly bound to the residual phase, as shown by the
high value of the IR parameter (Figure 9). Immediately after its addition to the soil,
Cr was mostly bound to the organic matter fraction (Figure 4). During incubation,
small amounts of Cr were further transferred from the CARB and ERO fractions to
the OM fraction at all levels of addition in both soils. Previous studies showed that
chromium is generally found in the residual phase followed by the oxide phase
in non-amended and in sludge-amended soils (Chang et al., 1984; McGrath and
Cegarra, 1992). Slow transformation from the CARB fraction into OM fraction
was also observed under the saturation moisture regime (Han and Banin, 1997).
This indicates that Cr was preferentially bound to the organic matter fraction in the
present extraction protocol. The reduced partition index (IR ) in the amended soils
slowly increased with time during incubation, which showed that Cr was slowly
transferred into the more stable fractions in the soil. However, even after one year of
incubation, Cr in the soils still remained removed from its initial quasi-equilibrium
partition pattern (Figure 10).

238

F. X. HAN AND A. BANIN

Figure 3. Changes of Cd fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

239

Figure 4. Changes of Cr fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

240

F. X. HAN AND A. BANIN

Figure 5. Changes of Cu fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

241

Figure 6. Changes of Ni fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

242

F. X. HAN AND A. BANIN

Figure 7. Changes of Pb fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

243

Figure 8. Changes of Zn fractions in two soils during 336 days of incubation at the field capacity
moisture regime.

244

F. X. HAN AND A. BANIN

Figure 9. The reduced partition index, IR , of six metals in two soils at various heavy metals loading
levels.

3.2.3. Copper
Added Cu in the soil, particularly at high loading levels, was initially bound to the
CARB and EXC fractions in the loessial soil and the CARB and OM fractions in
the sandy soil (Figure 5). Relatively high Cu concentrations were initially found
in the EXC fraction of the loessial soil at higher loading levels. After one year of
incubation, Cu was bound in the CARB, ERO and OM fractions of the sandy soil,
and the CARB and ERO fractions of the loessial soil. Previous studies showed that
the organically-bound and carbonate fractions were the major solid-phase forms of
Cu in soils amended with sludge, sulfate salts and Cu-enriched manure, or contaminated with mine tailings (Emmerich et al., 1982; Payne et al., 1988; McGrath and
Cegarra, 1992; McLaren and Ritchie, 1993). We have found that during incubation
Cu slowly returned to the native soil quasi-equilibrium state in both the sandy and
the loessial soils (Figure 10). Immediately after metal addition at high loading level
(5T), Ut s reached values of up to 5 and 25 in the sandy and loessial soils,
respectively, indicating high perturbation of metal partition in the soil. After one
year of incubation Ut s values decreased to 23 in both soils, indicating a return
to a distribution pattern more similar to the untreated soil. During incubation at
field capacity moisture Cu was transferred into the ERO, OM and, to some extent,
the RO fractions, whereas during incubation at water-saturated conditions, Cu was
transferred from the EXC fraction into the RO and CARB fractions (Han and
Banin, 1997).

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

245

Figure 10. The long-term changes of Ut s of metals (Equation (4)) in two soils during incubation at the field capacity moisture regime (Ut s of Cd and Pb are
not shown since analyses of their concentrations in the native soils were erratic due to analytical problems).

246

F. X. HAN AND A. BANIN

3.2.4. Nickel
Originally, Ni was mostly bound in the residual fraction of the non-amended native
soils. Added soluble Ni was bound to the CARB, EXC and ERO fractions during
the first stage of rapid equilibrium (Figure 6). During the prolonged incubation at
the field capacity moisture regime, Ni was slowly transferred from the EXC and
CARB fractions into the ERO and OM fractions. Under saturated conditions (Han
and Banin, 1997), added Ni was transferred from the EXC and CARB fractions
mainly into the RO fraction in the loessial soil and into the OM and ERO fractions
in the sandy soil. This indicates that incubation in the saturated regime resulted
in more pronounced transformation of Ni to the stable fractions than in the field
capacity regime. At low loading levels, Ut s approached 1.0 in both soils with time
(Figure 10). At higher loading levels Ut s stabilized at values of 34. Previous
studies have also shown that Ni distribution departed from the original partition
pattern of the control soil after addition of sludge but slowly returned towards the
distribution characteristics of the non-amended soil (McGrath and Cegarra, 1992).
3.2.5. Lead
Native Pb was found mainly in the RES and RO fractions in the untreated sandy
soil, and in the CARB and RES fractions in the loessial soil (Figure 7). During
incubation at the field capacity moisture regime, small amounts of Pb were transferred from the CARB fraction into the ERO fraction but generally the distribution
pattern did not change and the majority of Pb remained bound to the CARB fraction. Lead in arid-zone soils has a relatively small IR due to its presence, mainly,
in the carbonate fraction while in humid-zone soils Pb may have higher IR values
since a larger fraction of the metal is bound to organic matter and Fe oxides (Jin et
al., 1996).
3.2.6. Zinc
In the untreated soils Zn was mainly present in the RES, RO and CARB fractions,
with significantly higher proportion of Zn bound to the RES fraction of the loessial
soil (Figure 8). Zinc in the non-amended loessial soil was transferred from the
RO fraction to the CARB fraction during incubation, similar to the observations in
the saturated soils (Han and Banin, 1997). Added Zn in both soils was initially
attached to the CARB (and EXC) fractions, and during incubation at the field
capacity moisture it was transferred to the ERO and, to some extent, to the OM
and RO fractions. Under saturation, added Zn moved along a different pathway
and was transferred from the EXC, CARB and even the ERO fractions, to the RO
fraction in the loessial soil, and from the EXC and CARB fractions to the OM,
RO and ERO fractions in the sandy soil (Han and Banin, 1997). Zinc partition as
measured by the IR index was affected by the properties of the soil and the total
metal content (Figure 9). At equal total metal content, Zn was more strongly bound
in the loessial soil (as were most metals). The Ut s function of Zn initially reached
very high values, mainly due to the high loadings of this metal added to the soils.

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

247

With time the Ut s value decreased but remained high, particularly in the sandy soil
at the 3T and 5T addition levels (Figure 10).
3.3. OVERVIEW

OF THE TRANSFORMATIONS OF METALS DURING

INCUBATION

The results show in general that heavy metals added to the two soils, which were
then incubated at field capacity moisture, were slowly redistributed with time,
tending to return to a solid-phase fractional distribution pattern similar to that of
the incubated untreated soils. The overall metal distribution in the untreated soils
is therefore addressed first, followed by analysis of the transfer and transformation
processes in the metal-amended soils.
3.3.1. Untreated soils
The native distribution of the metals in the two soils was largely dependent upon
the nature of the metal and the soil properties (Han and Banin, 1997). Native Cu,
Cr and Ni resided predominantly in the RES, RO and OM fractions and native
Zn was mainly found in the RES and RO fractions. Cadmium in the loessial soil
was mostly present in the CARB and EXC fractions. During incubation at the
field capacity moisture, native Cd, Cu, Ni and Zn were transferred to the CARB
fraction (Figures 38). The main source for Cu, Ni and Zn was the RO fraction.
These transformations increased the lability of these metals in the untreated soils
following prolonged incubation at the field capacity moisture regime. The native Cr
and Pb distributions have not changed considerably during prolonged incubation.
In comparison, incubation of the untreated soils in saturated conditions resulted in
higher proportion of Cu, Ni and Zn in the CARB fraction than in the field capacity
incubation, while Cd underwent the same change in both moisture regimes, and
the distribution of native Cr and Pb did not change significantly in either moisture
regime (Han and Banin, 1997).
3.3.2. Metal-amended soils
The metals, added in soluble form, were transferred from the most labile fraction
(EXC) to the more stable fractions. The transformation involved an initial (< 1 hr)
rapid process followed by a slow long-term process. At low levels of addition, the
trend was towards a fractional distribution more similar to that of the untreated soil,
even though the total metal concentration in the soil increased. At higher levels, the
soils did not fully return to the distribution characterizing the untreated soil.
The reduced partition index (IR ) of the six metals in the two soils, measured
1 h after metal addition, decreased with increasing metal concentration due to the
presence of higher proportions of metals in the more labile fractions of the soil
(Figure 9). Differences in the binding-intensity of the metals are clearly shown, as
modulated by the nature of the soil. At a given total concentration, IR of all metals
is generally higher in the loessial soil. Comparing IR for five metals, each at a total

248

F. X. HAN AND A. BANIN

concentration of 50 mg kg1 , we find the following ordering: Sandy soil: Cr > Cu

> Zn > Pb > Ni; Loessial soil: Cr > Zn > Ni > Cu > Pb. Cadmium, at much lower
total metal concentration range, generally had the lowest IR value, indicating its
lability in the soil and the lack of strong binding mechanisms for this metal to the
solid-phase of soils (Han and Banin, 1997). Lead tended to have relatively low IR
values in both soils, mainly reflecting the fact that Pb was mostly present in the
carbonate fraction. This behavior is different from that of Pb in many humid-zone
soils, where higher proportion of Pb is bound to organic matter and iron oxides,
resulting in relatively high overall binding strength (Jin et al., 1996).
The redistribution and transformation of added metals in soils is affected by
three factors: the distribution of the metals in the native soil, the metal loading
level and the time since metal addition (Han and Banin, 1997). The Ut s function
(Equation (4)) was used to describe the removal from, or attainment of, equilibrium
of the incubated metal-amended soil in comparison to the incubated non-amended
control soil (Figure 10). The initial value of Ut s for Cr, Cu, Ni and Zn is high due to
the major perturbation of the quasi-equilibrium in the native soil by the addition of
the soluble metals. In general, Ut s declined with time, indicating tendency to return
to the pattern of distribution of the untreated soil. At low metal-loading levels, such
as in the 0.5T treatment, the Ut s of the soil rapidly approached the value of one,
indicating that the redistribution was relatively fast and followed the pattern of the
untreated soils. At the intermediate (2T) and higher levels of addition (3T and 5T),
the amended soils were still far from the distribution in the incubated non-amended
soil, but they were slowly approaching such state with time.
Within the first one hour from the start of incubation under the field capacity
regime and/or during the SSD procedure itself, added soluble Cd, Pb, Ni, Zn, and
to some extent Cu, were transferred from the EXC fraction mainly into the CARB
fraction (6075% for Cd, 6570% for Pb, 4050% for Ni, 5570% for Zn and 30
40% for Cu). Added Cr in both soils, and to some extent Cu and Ni in the sandy
soil, were mainly incorporated into the OM fraction (4070% Cr, and 2030% for
both Ni and Cu in the sandy soil). Chromium, and to some extent, Cu and Ni, were
more preferentially bound than other metals to the organic matter fraction. These
data show that soils at field capacity underwent the same fast transfer process from
the EXC (including soluble) fraction into the more stable fractions as observed
under the saturated paste regime (Han and Banin, 1997). This transfer is partly
related to rapid equilibration of the added soluble metals with the soil solids during
the first step of the SSD procedure. However, significant amounts of Ni, Cd, and Cu
still remained in the EXC fraction after one hour of incubation in the field capacity
regime.
Redistribution of metals did not stop in the soils and continued during one year
of incubation under the field capacity regime by long-term metal transformation
processes. Heavy metals were slowly transferred among solid-phase components
as shown in Figures 38. It was observed that added Cu, Ni and Zn were transferred
from the EXC and CARB fractions into the ERO and OM fractions, (Zn mainly

TRANSFORMATIONS OF HEAVY METALS IN SOILS AT FIELD CAPACITY MOISTURE

249

into the ERO fraction), Cr and Pb moved from the CARB fraction into the OM
and ERO fractions, respectively, and Cd moved from the EXC fraction into the
CARB fraction. These processes were driven by reactions of the metals with the
more stable solid-phase components of the soils and slow incorporation within
these components.
3.4. T HE

EFFECT OF MOISTURE REGIME

It was observed that Cd and Cr underwent the same pathways of slow transformation in arid-zone soils under both the field capacity and the moisture-saturation
regimes, whereas Cu, Ni, and Zn followed somewhat different pathways of transformations under the two regimes. In the field capacity regime, added soluble Cu,
Ni and Zn were slowly transferred mainly and preferentially into the ERO (Mn
oxides) fraction and to some extent into the OM, RO and RES fractions (present
study). In the moisture-saturated regime, these metals were transferred into the RO
fraction, followed by the OM and ERO fractions, especially at the higher loading
levels (Han and Banin, 1997). The main cause for this difference appears to be that
in saturated soils Mn(IV) from MnO2 was reduced to Mn(II) and transferred into
the EXC and CARB fractions in the initial stage of incubation (Han and Banin,
1996). This decreased the binding capacity of the ERO fraction for heavy metals in
the saturated soils, and the metals were transferred into the RO and OM fractions.
In contrast, soils incubated at the field capacity regime were more oxic and Mn(IV)
was not reduced while some Mn(II) was transferred from the CARB fraction into
the ERO fraction, thus increasing the ERO capacity to bind heavy metals such as
Cu, Ni and Zn.
4. Summary
The soil water regime affected the pathways and kinetics of transformation of
added heavy metals during incubation of one year. The effect depended on the
chemical nature of the metals and on soil properties. During prolonged incubation
at the field capacity moisture, added Cu, Ni and Zn were transferred into the ERO,
OM and RO fractions, Cr was transferred into the OM fraction, and Cd remained
mainly bound to the CARB fraction. On the other hand, during prolonged incubation at saturated conditions, Cu, Ni and Zn were mainly transferred to the RO
and OM fractions, while Cd and Cr generally followed the same transformation
pathways as in the field capacity regime.
The present study shows that heavy metals added to soils in soluble form are
slowly transferred and partitioned among the solid-phase components of the soil
according to the native pattern of distribution. The distribution is characteristic of
the given soil and the given element, and strongly depends on the soil properties.
The results support the hypothesis that soils tend to return to the fractional quasiequilibrium state of the non-amended soil in both water regimes, as long as the

250

F. X. HAN AND A. BANIN

loading level is not excessively high compared to the native content of metals in
the soil.

Acknowledgments
This study was supported in part by funds from the Ministry of Science and the
Arts, Israel, and the European Community (ISC-8911 ISR (ENV) #3006), and from
the Austrian Friends of the Hebrew University of Jerusalem (Poject 0306160).

References
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Report. No. of Project: Wt 8687/458.
Beckett, P. H. T.: 1989, Adv. Soil Sci. 9 143.
Chang, A. C., Page, A. L., Warneke, J. E. and Grgurevic, E.: 1984, J. Environ. Qual. 13, 33.
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